CN104017212B - A kind of polyimide resin and preparation method thereof and a kind of polyimide foam - Google Patents
A kind of polyimide resin and preparation method thereof and a kind of polyimide foam Download PDFInfo
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- CN104017212B CN104017212B CN201310066152.7A CN201310066152A CN104017212B CN 104017212 B CN104017212 B CN 104017212B CN 201310066152 A CN201310066152 A CN 201310066152A CN 104017212 B CN104017212 B CN 104017212B
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Abstract
The invention provides a kind of polyimide resin, containing Formulas I, Formula II or the construction unit shown in formula III in described polyimide resin.Present invention also offers the preparation method of described polyimide resin, including R1(NH2)3, polylactide, dianhydride add in solvent, remove solvent after reaction, obtain described polyimide resin.Finally, present invention also offers a kind of polyimide foam, by the broken rear tabletting of the polyimide resin powder present invention provided, then foamable obtains.The polyimide resin of confession of the present invention, contained imide structure unit has good reactivity, available good heat stability, chemical stability, mechanical performance, the polyimide foam that service life is longer after foamable.
Description
Technical field
The invention belongs to polyimide material field, particularly relate to a kind of polyimide resin and preparation method thereof and one
Polyimide foam.
Background technology
Along with the appearance of polymer artificial synthetic material, porous material is used widely in synthetic plastic industry, all kinds of
Foam plastics is seen everywhere.For the transmission foamed materialss such as polyurethane, polyethylene, polystyrene, polyimides steeps
Foam has heat resistance, high temperature barrier, noise reduction, impact resistance, dimensional stability, wave transparent performance and the anti-flammability of excellence
Can, can be as heat insulation, sound insulation and fire resistance, in fields such as aircraft, spacecraft, weaponry, naval vessel, bullet train and automobiles
Application.
At present, the polyimide foam used in prior art, generally by methacrylic acid and methacrylonitrile
In monomer mixture add fatty alcohol as foaming agent carry out foaming prepare.But due to methacrylic acid and methacrylonitrile this two
Planting monomer and all may occur from body polymerization, the acid imide rate causing the two is relatively low, and the use temperature of the foamed materials obtained is relatively low,
Mechanical performance is the most poor.
Summary of the invention
The present invention solves the polyimide foam prepared in prior art by methacrylic acid and methacrylonitrile monomers
Exist and use that temperature is low, the technical problem of bad mechanical property, propose a kind of novel polyimide resin and preparation method thereof and
A kind of polyimide foam.
Specifically, the invention provides a kind of polyimide resin, in described polyimide resin containing Formulas I, Formula II or
Construction unit shown in formula III:
Formulas I:
Formula II:
Formula III:
Wherein, X isN is the integer of 20～50；
R1For
R2Any one in O, S or having structure:
Present invention also offers the preparation method of described polyimide resin, including by R1(NH2)3, polylactide, dianhydride
Add in solvent, remove solvent after reaction, obtain described polyimide resin；
Wherein, described dianhydride is
Finally, the invention provides a kind of polyimide foam, described polyimide foam is by providing the present invention
The broken rear tabletting of polyimide resin powder, then foamable obtains.
The polyimide resin that the present invention provides, contained imide structure unit has good reactivity, its
The homodisperse nanometer foam of generation can be decomposed when foamable, thus obtain the polyimide foam that the present invention provides, should
Polyimide foam the most also has good heat stability, chemical stability, mechanical performance, and service life is longer.With
Time, in the preparation method of the polyimide resin that the present invention provides, by synthesis material (is included aromatic amine R1(NH2)3, poly-
Lactide and dianhydride) species structure carry out specifically chosen, it is ensured that there is during reaction higher acid imide rate.
Detailed description of the invention
The invention provides a kind of polyimide resin, containing Formulas I, Formula II or formula III institute in described polyimide resin
The construction unit shown:
Formulas I:
Formula II:
Formula III:
Wherein, X isN is the integer of 20～50；
R1For
R2Any one in O, S or having structure:
The polyimide resin that the present invention provides, contained imide structure unit has good reactivity, its
The homodisperse nanometer foam of generation can be decomposed when foamable, thus obtain the polyimide foam that the present invention provides, should
Polyimide foam the most also has good heat stability, chemical stability, mechanical performance, and service life is longer.
In the present invention, the glass transition temperature of described polyimide resin is more than 300 DEG C, even more than 350 DEG C,
Thus can ensure that when subsequent heat foams, resin will not occur serious softening transform.Accordingly, the number of described polyimide resin
Average molecular weight is 70000～500000.
As a kind of preferred implementation of the present invention, R1ForR2ForBut it is not limited to
This.
Present invention also offers the preparation method of described polyimide resin, including by R1(NH2)3, polylactide, dianhydride
Add in solvent, remove solvent after reaction, obtain described polyimide resin；
Wherein, described dianhydride is(pyromellitic acid anhydride),
Wherein, aromatic amine R1(NH2)3The following formula IV of structure shown in, it is three amine structures, specially Formula V or Formula IV institute
The compound shown.In the present invention, described aromatic amine R1(NH2)3Preferably employing the compound shown in Formula V, it is three (4-amino
Phenyl) amine (being called for short TAPA), but it is not limited to this.
Polylactide, has another name called polylactic acid, and its structural formula is
Preparation in accordance with the present invention, aromatic amine R1(NH2)3First react in a solvent with polylactide, reaction
Mechanism is:
Wherein,It is
Above-mentioned reaction is carried out in a solvent, and described solvent is the various solvents that those skilled in the art commonly use, the most optional
From N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAc), dimethyl sulfoxide, sulfolane, dioxane, N-
In N-methyl-2-2-pyrrolidone N (NMP), NVP, metacresol, benzene,toluene,xylene, oxolane one
Plant or multiple, but be not limited to this.
Preparation in accordance with the present invention, then dianhydride continues to react with above-mentioned product, reaction machine now
Manage and include following three classes according to the variety classes of dianhydride:
In the present invention, described aromatic amine R1(NH2)3It is 1:0.8～1.2:0.98 with the mol ratio of polylactide, dianhydride
～3.15.Under preferable case, the response time is 2～12h.
As a kind of preferred implementation of the present invention, it is additionally included in course of reaction and controls the viscosity of reaction system and be
The step of 10000-100000cP.For improving the conversion ratio (i.e. improving acid imide rate) of above-mentioned reaction further, it is additionally included in
Course of reaction controls the step that solid content is 10-60wt% of reaction system.
As it was previously stated, R1It is preferablyNow corresponding aromatic amine is three (4-aminophenyls)
(compound shown in Formula V).R2It is preferablyNow corresponding dianhydride is 3,3 ', 4, and 4 '-benzophenone tetracarboxylic dianhydride, its knot
Shown in the following Formula VII of structure.
In the preparation method of the polyimide resin that the present invention provides, by synthesis material (is included aromatic amine R1
(NH2)3, polylactide and dianhydride) structure carry out preferably, it is ensured that there is during reaction higher acid imide rate.
Finally, the invention provides a kind of polyimide foam, described polyimide foam is by providing the present invention
The broken rear tabletting of polyimide resin powder, then foamable obtains.
The step of described foamable is the common knowledge of those skilled in the art.As it was previously stated, present invention raising is poly-
The glass transition temperature of imide resin is more than 300 DEG C, polyimide resin generation softening transform during for preventing from foaming, because of
The temperature of this foamable is unsuitable too high.Under preferable case, the step of described foamable includes: first pre-at 80～120 DEG C
Heat 10～30min, then at 150～180 DEG C, heat 3～15min, in 30min, then it is warming up to 300～350 DEG C and keeps 5
～25min, in 10min, finally it is warming up to 380～400 DEG C and keeps 5～25min, obtaining described polyimide foam.
In foaming process, polyimide resin thermally decomposes, and produces noble gas, thus is formed all in resin structure
The bubble structure of even distribution, in this bubble structure, rear extended meeting is filled by air, i.e. obtains described polyimide foam.Due to air
It is the material that dielectric constant is minimum, so the dielectric constant of the Polyimide foams obtained is relatively low.Described polyimides
The density of foam is 0.03-0.10g/cm3, relative dielectric constant is less than 3.0.
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with
Embodiment, is further elaborated to the present invention.Should be appreciated that specific embodiment described herein is only in order to explain
The present invention, is not intended to limit the present invention.Employed in embodiment i.e. comparative example, raw material is all commercially available.
Embodiment 1
(1) solvent DMF accurately weighing 350mL is placed in there-necked flask, adds the aromatic amine (TAPA) of 28.55g, adds
Hot reflux 1h, be subsequently adding the dianhydride (pyromellitic acid anhydride) of 21.46g and 177.21g polylactide (molecular weight 1962,
I.e. n=27), i.e. aromatic amine, polylactide is 1:0.9:1 with the mol ratio of dianhydride, reacts 4h.Then reduce pressure distillation, remove
Solvent, continues vacuum drying, obtains the faint yellow polyimide resin solid of the present embodiment, be designated as S1, and it contains shown in Formulas I
Construction unit, wherein R1ForX is
(2) S1 is pulverized, and be at room temperature pressed into thin slice, at 120 DEG C, preheat 30min, then heat at 180 DEG C
5min, is warming up to 330 DEG C in 30min and keeps 10min, is finally warming up to 400 DEG C in 10min and keeps 10min, i.e. obtains this
The polyimide foam S10 of embodiment.
Embodiment 2
Method same as in Example 1 is used to prepare the polyimide resin S2 and polyimide foam S20 of the present embodiment,
Difference is:
In step (1), useAs in the dianhydride alternate embodiment 1 of the present embodiment
Pyromellitic acid anhydride, and the mol ratio of TAPA, polylactide (molecular weight is 1962, i.e. n=27) and dianhydride is 1:0.9:
1.2；
The polyimide resin S2 obtained by above-mentioned steps, is obtained it and contains the construction unit shown in Formula II, wherein R1
ForX is
Embodiment 3
Method same as in Example 1 is used to prepare the polyimide resin S3 and polyimide foam S30 of the present embodiment,
Difference is:
In step (1), useAnd R2ForDianhydride as the present embodiment
Pyromellitic acid anhydride in alternate embodiment 1, and TAPA, polylactide (molecular weight is 1962, i.e. n=27) rub with dianhydride
That ratio is 1:0.9:3；
The polyimide resin S3 obtained by above-mentioned steps, is obtained it and contains the construction unit shown in formula III, wherein R1
ForX isR2For
Embodiment 4
Method same as in Example 1 is used to prepare the polyimide resin S4 and polyimide foam S40 of the present embodiment,
Difference is:
In step (1), aromatic amine R1(NH2)3Middle R1ForDianhydride structural formula isAnd R2For(molecular weight is for aromatic amine, polylactide
1458, i.e. n=20) it is 1:1:1 with the mol ratio of dianhydride；
The polyimide resin S4 obtained by above-mentioned steps, is obtained it and contains the construction unit shown in formula III,
Wherein R1ForX isR2For
Embodiment 5
Method same as in Example 1 is used to prepare the polyimide resin S5 and polyimide foam S50 of the present embodiment,
Difference is:
In step (1), aromatic amine R1(NH2)3Middle R1ForDianhydride structural formula isAnd R2ForAromatic amine, polylactide (divide
Son amount is 3618, i.e. n=50) it is 1:1:2.5 with the mol ratio of dianhydride；
The polyimide resin S5 obtained by above-mentioned steps, is obtained it and contains the construction unit shown in formula III, wherein R1
ForX isR2For
Comparative example 1
330g isopropanol and 100g Methanamide are joined by 5700g methacrylic acid, 4380g methyl-prop as foaming agent
Alkene nitrile and 31g propyl methacrylate composition mixture in, by this mixture at 40 DEG C by two a size of 50*50cm
Glass plate and the chamber that formed of the thick edge seal thing of 18.5mm in be polymerized 68h.Polymerizate is then subjected to from 32 DEG C to 115 DEG C
Heating schedule 32h, complete final polyreaction；Then foamable 2h25min at 205 DEG C.
By above-mentioned steps, obtain the polyimide foam DS10 of this comparative example.
Performance test
(1) density measurement
With reference to GB1033 plastic density and relative density method of testing, use pycnometric method to polyimide foam S10-
S50 and DS10 tests.
(2) dielectric constant
With reference to GB/T1408.1 insulant electrical strength test method, use dielectrometer that polyimides is steeped
Foam S10-S50 and DS10 tests.
(3) mechanical property
With reference to GB/T1040 plastic tensile method for testing performance, GB/T9341 plastics bend test method, use electronics ten thousand
Polyimide foam S10-S50 and DS10 can be tested testing machine.
Test result is as shown in table 1.
Table 1
From the test result of upper table 1 it can be seen that the polyimide foam S10-S50 density that the present invention provides is 0.032
～0.908g/cm3, dielectric constant is less than 3.0, has good mechanical property, hence it is evident that be better than the foam sample of comparative example simultaneously
DS10, therefore its service life is also the longest.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Any amendment, equivalent and the improvement etc. made within god and principle, should be included within the scope of the present invention.
Claims (10)
1. a polyimide resin, it is characterised in that containing shown in Formulas I, Formula II or formula III in described polyimide resin
Construction unit:
Formulas I:
Formula II:
Formula III:
Wherein, X isN is the integer of 20～50；
R1For
R2Any one in O, S or having structure:
Polyimide resin the most according to claim 1, it is characterised in that the number-average molecular weight of described polyimide resin
It is 70000～500000.
Polyimide resin the most according to claim 1, it is characterised in that R1ForR2For
4. the preparation method of the polyimide resin described in claim 1, it is characterised in that include R1(NH2)3, poly-third hand over
Ester, dianhydride add in solvent, remove solvent, obtain described polyimide resin after reaction；
Wherein, described dianhydride is
Preparation method the most according to claim 4, it is characterised in that described solvent is selected from DMF, N,
N-dimethyl acetylamide, dimethyl sulfoxide, sulfolane, dioxane, METHYLPYRROLIDONE, N-vinyl-2-pyrrolidine
One or more in ketone, metacresol, benzene,toluene,xylene, oxolane.
Preparation method the most according to claim 4, it is characterised in that R1(NH2)3With the mol ratio of polylactide, dianhydride it is
1:0.8～1.2:0.98～3.15, the time of reaction is 2～12h.
Preparation method the most according to claim 4, it is characterised in that be additionally included in course of reaction and control reaction system
Viscosity is the step of 10000-100000cP.
8. according to the preparation method described in claim 4 or 7, it is characterised in that be additionally included in course of reaction control reactant
The step that solid content is 10-60wt% of system.
9. a polyimide foam, it is characterised in that described polyimide foam is by sub-by the polyamides described in claim 1
Tabletting after polyimide resin pulverizing, then foamable obtains.
Polyimide foam the most according to claim 9, it is characterised in that the step of described foamable includes: first exist
Preheat 10～30min at 80～120 DEG C, then at 150～180 DEG C, heat 3～15min, in 30min, be then warming up to 300
～350 DEG C and keep 5～25min, in 10min, finally it is warming up to 380～400 DEG C and keeps 5～25min, obtaining described poly-
Acid imide foam.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310066152.7A CN104017212B (en) | 2013-02-28 | 2013-02-28 | A kind of polyimide resin and preparation method thereof and a kind of polyimide foam |
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| CN201310066152.7A CN104017212B (en) | 2013-02-28 | 2013-02-28 | A kind of polyimide resin and preparation method thereof and a kind of polyimide foam |
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| CN104017212B true CN104017212B (en) | 2016-12-28 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101107291A (en) * | 2005-01-21 | 2008-01-16 | 三菱瓦斯化学株式会社 | Polyimide resin, polyimide film, and polyimide laminate |
| CN102267940A (en) * | 2011-05-31 | 2011-12-07 | 湖北大学 | Synthesis of triamine containing symmetrical triaryl pyridine structure and hyperbranched polyimide thereof |
-
2013
- 2013-02-28 CN CN201310066152.7A patent/CN104017212B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101107291A (en) * | 2005-01-21 | 2008-01-16 | 三菱瓦斯化学株式会社 | Polyimide resin, polyimide film, and polyimide laminate |
| CN102267940A (en) * | 2011-05-31 | 2011-12-07 | 湖北大学 | Synthesis of triamine containing symmetrical triaryl pyridine structure and hyperbranched polyimide thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Novel Organosoluble Aromatic Polyimides Bearing Pendant";CHA-WEN CHANG等;《Journal of Polymer Science: Part A: Polymer Chemistry》;20081215;第46卷;第7937-7949页 * |
| "Preparation and Properties of Novel Soluble Aromatic Polyimides from 4,4-Diaminotriphenylamine and Aromatic Tetracarboxylic Dianhydrides";YOSHlYUKl OISHI等;《Journal of Polymer Science》;19920531;第30卷(第6期);第1027-1035页 * |
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